Quinolinyldiamido transition metal complexes, production and use thereof

Abstract

Quinolinyldiamido transition metal complexes are disclosed for use in alkene polymerization to produce multimodal polyolefins.

What is claimed is: 
     
       1. A quinolinyldiamido transition metal complex represented by Formula II: 
       
         
           
           
               
               
           
         
         wherein:
 M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 metal; 
 X is an anionic leaving group; 
 L is a neutral Lewis base; 
 R 1  and R 13  are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups; 
 R 2 , R 3 , R 4 , R 5 , and R 6  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino; 
 n is 1 or 2; 
 m is 0, 1, or 2; 
 n+m is not greater than 4; and 
 any adjacent R groups (e.g., R 1  & R 2 , R 2  & R 3 , etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings; 
 any two X groups may be joined together to form a dianionic group; 
 any two L groups may be joined together to form a bidentate Lewis base; and 
 an X group may be joined to an L group to form a monoanionic bidentate group, 
 E is carbon, silicon, or germanium; 
 R 7  through R 9  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and 
 any two R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings, 
 R 12  is selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, 
 R 10  and R 11  are independently selected from the group consisting of hydrocarbyls and substituted hydrocarbyls, 
 where R 10  and R 11  are joined to form a substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings. 
 
       
     
     
       2. A quinolinyldiamido transition metal complex represented by Formula (II): 
       
         
           
           
               
               
           
         
         wherein:
 M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal; 
 X is an anionic leaving group; 
 L is a neutral Lewis base; 
 R 1  and R 13  are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups; 
 R 2 , R 3 , R 4 , R 5 , and R 6  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino; 
 n is 1 or 2; 
 m is 0, 1, or 2 
 n+m is not greater than 4; and 
 any two adjacent R groups (e.g. R 1  & R 2 , R 2  & R 3 , etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings; 
 any two X groups may be joined together to form a dianionic group; 
 any two L groups may be joined together to form a bidentate Lewis base; and 
 an X group may be joined to an L group to form a monoanionic bidentate group, 
 E is carbon, silicon, or germanium; 
 R 7  and R 8  are independently selected from the group consisting of hydrocarbyls and substituted hydrocarbyls, 
 R 9  through R 12  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and 
 and any two R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings, 
 where R 7  and R 8  are joined to form a substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings. 
 
       
     
     
       3. The complex of  claim 1 , wherein E is carbon. 
     
     
       4. The complex of  claim 2 , wherein E is carbon. 
     
     
       5. The complex of  claim 2 , wherein M is Ti, Zr, of Hf. 
     
     
       6. The complex of  claim 1 , wherein M is Ti, Zr, or Hf. 
     
     
       7. The complex of  claim 1 , wherein R 2 , R 3 , R 4 , R 5 , and R 6  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen. 
     
     
       8. The complex of  claim 2 , wherein R 2 , R 3 , R 4 , R 5 , and R 6  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen. 
     
     
       9. The complex of  claim 1 , wherein each L is independently selected from Et 2 O, MeOtBu, Et 3 N, PhNMe 2 , MePh 2 N, tetrahydrofuran, and dimethylsulfide. 
     
     
       10. The complex of  claim 2 , wherein each L is independently selected from Et 2 O, MeOtBu, Et 3 N, PhNMe 2 , MePh 2 N, tetrahydrofuran, and dimethylsulfide. 
     
     
       11. The complex of  claim 1 , wherein each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido. 
     
     
       12. The complex of  claim 2 , wherein each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido. 
     
     
       13. The complex of  claim 1 , wherein R 1  is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl. 
     
     
       14. The complex of  claim 2 , wherein R 1  is 2,6-diisopropylphenyl, 2,4,6-triisoproplphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl. 
     
     
       15. The complex of  claim 1 , wherein R 13  is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorphenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl. 
     
     
       16. The complex of  claim 2 , wherein R 13  is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl. 
     
     
       17. The complex of  claim 1 , wherein R 1  is 2,6-diisopropylphenyl and R 13  is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms. 
     
     
       18. The complex of  claim 2 , wherein R 1  is 2,6-diisopropylphenyl and R 13  is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms. 
     
     
       19. The complex of  claim 2 , wherein R 10  and R 11  are joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings. 
     
     
       20. The complex of  claim 2 , wherein R 10  and R 11  are joined to form a substituted or unsubstituted saturated hydrocarbyl ring, where the ring has 6 ring atoms and where substitutions on the ring can join to form additional rings. 
     
     
       21. A catalyst system comprising an activator and the transition metal complex of  claim 1 . 
     
     
       22. The catalyst system of  claim 21 , wherein the activator is an alumoxane. 
     
     
       23. The catalyst system of  claim 21 , wherein the activator is a non-coordinating anion. 
     
     
       24. The catalyst system of  claim 21 , wherein the catalyst complex and/or the activator is supported. 
     
     
       25. A polymerization process to produce polyolefin comprising contacting one or more olefin monomers with the catalyst system of  claim 21  and obtaining olefin polymer. 
     
     
       26. A polymerization process to produce polyolefin comprising contacting, in solution phase, one or more olefin monomers with a catalyst system comprising the complex of  claim 1  and activator, at a temperature of at least 85° C., and obtaining olefin polymer, where the olefin monomers comprise ethylene and propylene. 
     
     
       27. The process of  claim 25 , wherein the monomers comprise ethylene. 
     
     
       28. The process of  claim 25 , wherein the monomers comprise propylene. 
     
     
       29. The process of  claim 25 , wherein the polymerization process is a solution process. 
     
     
       30. The process of  claim 25 , wherein the polyolefin produced is an ethylene polymer. 
     
     
       31. The process of  claim 28 , wherein the polyolefin produces is isotactic polypropylene. 
     
     
       32. A catalyst system comprising the activator and the transition metal complex of  claim 2 . 
     
     
       33. The catalyst system of  claim 21 , wherein M=Hf, Zr, or Ti. 
     
     
       34. The catalyst system of  claim 32 , wherein M=Hf, Zr, or Ti. 
     
     
       35. A polymerization process to produce olefin comprising contacting, in solution phase, one or more olefin monomers with a catalyst system comprising the complex of  claim 2  and activator, at a temperature of at least 85° C., and obtaining olefin polymer, where the olefin monomers comprise ethylene and propylene and the olefin polymer has a melt flow rate (230° C., 2.16 kg) of less than 1.0 dg/min. 
     
     
       36. The polymerization process of  claim 26 , wherein the activator is a non-coordinating anion. 
     
     
       37. The complex of  claim 1 , wherein R 10  and R 11  are joined to form a five membered ring with the joined R 10 R 11  group being —CH 2 CH 2 —. 
     
     
       38. The complex of  claim 1 , wherein R 10  and R 11  are joined to form a six membered ring with the joined R 10 R 11  group being —CH 2 CH 2 CH 2 —. 
     
     
       39. The complex of  claim 2 , wherein R 7  and R 8  are joined to form a six-membered aromatic ring with the joined R 7 R 8  group being —CH═CHCH═CH—. 
     
     
       40. The complex of  claim 2 , wherein M is Hf; R 2  to R 6  are H; X is NMe 2  or Me; n is 2; y is 0 and L is not present; R 1  is 2,6-diisopropylphenyl; R 13  is 2-methylphenyl, 2,6-dimethylphenyl, or phenyl; R 12  is H; R 11  forms a ring with R 10 ; R 9  is H; and R 7  and R 8  are joined together to form a six-membered aromatic ring. 
     
     
       41. A process to produce a quinolinyldiamide ligand comprising contacting compound (III) with compound (IV) to produce quinolinyldiaimine (V) in a coupling reaction, wherein compound (III), compound (IV) and the quinolinyldiaimine (V) are represented by the formula: 
       
         
           
           
               
               
           
         
         wherein;
 W* and Y* are each independently selected from boronic acid ester, halide, alkali metal, alkaline earth metal halide, zinc halide, zincate, and triflate; 
 E is carbon, silicon, or germanium; 
 R 1  and R 13  are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups; 
 R 2 , R 3 , R 4 , R 5 , and R 6  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino; 
 any two adjacent R groups (e.g. R 1  & R 2 , R 2  & R 3 , etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings; 
 R 7  through R 12  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and 
 any two R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings. 
 
       
     
     
       42. The process of  claim 41  wherein R 10  and R 11  are joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic-ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings. 
     
     
       43. A process to produce a transition metal quinolinyldiamide complex by reaction of quinolinyldiamine (V) with a metal reactant containing anionic basic leaving groups, wherein the quinolinyldiamine (V) is represented by the formula: 
       
         
           
           
               
               
           
         
         wherein;
 E is carbon, silicon, or germanium; 
 R 1  and R 13  are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups; 
 R 2 , R 3 , R 4 , R 5 , and R 6  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino; 
 any two adjacent R groups (e.g., R 1  & R 2 , R 2  & R 3 , etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings; 
 R 7  through R 12  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and 
 any two R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings. 
 
       
     
     
       44. A process to produce a dialkylated quinolinyldiamide complex by reaction of quinolinyldiamido complex (VI) with an organolithium, Grignard, or organoaluminum reagent, wherein quinolinyldiamido complex (VI) is represented by the formula: 
       
         
           
           
               
               
           
         
         wherein,
 X* is a halide, alkoxide, or dialkylamido; 
 E is carbon, silicon, or germanium; 
 R 1  and R 13  are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups; 
 R 2 , R 3 , R 4 , R 5 , and R 6  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino; 
 any two adjacent R groups (e.g., R 1  & R 2 , R 2  & R 3 , etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings; 
 R 7  through R 12  are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and 
 any two R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.